Materials Science in Semiconductor Processing 151 (2022) 106993

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Materials Science in Semiconductor Processing

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First principles study of structural, electronic, elastic and optical properties

of Cs2 LiTlBr6 and Cs2 NaTlBr6
M. Zia ur Rehman a , Shaimaa A.M. Abdelmohsen b , Eman A. Mahmoud c , M. Usman Saeed a ,
M. Idress a , M. Shafiq a , B. Amin a , Y. Saeed a ,∗
a
Department of Physics, Abbottabad University of Science and Technology, Abbottabad, KPK, Pakistan
b Department of Physics , College of Science, Princess Nourah bint Abdulrahman University, P.O. Box 84428, Riyadh 11671, Saudi Arabia
c Department of Food Industries, Faculty of Agriculture, Damietta University, Damietta, Egypt

ARTICLE INFO ABSTRACT

Keywords: New double perovskites materials, Cs2 B+1 B+3 X6 , where B+1 = Na, Li B+3 = Tl, Sb, Bi and X6 = Cl, Br are
DFT investigated under the framework of density functional theory (DFT) by applying all electron full-potential
ab initio study
linearized augmented plane wave (FP-LAPW+lo) technique. Without and with spin–orbit coupling (SOC) band
Optical properties
structures are calculated. Electronic charge density graph reveal the ionic nature of Cs-atom with Br-atom and
Thermodynamic stability
Bandgap
strong covalent bonding between Tl-atom and Br-atom. While band structures for Cs2 LiTlBr6 and Cs2 NaTlBr6
are calculated with mBJ+SOC for the correction of value of the bandgap relative to experimental value of
MAPI. Values of direct bandgap at 𝛤 -point are 1.817 eV for Cs2 LiTlBr6 and 1.827 eV for Cs2 NaTlBr6 that are
close to the bandgap of 1.55 eV of parent organic–inorganic perovskite CH3 NH3 PbI3 (MAPI). Effective mass of
electron (m*𝑒 ) for Cs2 LiTlBr6 and Cs2 NaTlBr6 are 0.671 and 0.724 respectively which are less than that of Si
(1.09). Therefore it is expected that the carrier mobility of both materials is greater than Si. In order to study
the contribution of orbits of Cs, Li, Na, Tl and Br close by the Fermi level, we examined the total and partial
density of states. The optical properties were study to investigate the absorption coefficient of both materials.
Studies of the thermodynamics and elastic characteristics along with phonon dispersion confirms that these
two materials are stable. Because of stable, direct bandgap and a value of the bandgap closer as MAPI the
materials Cs2 LiTlBr6 and Cs2 NaTlBr6 are significant competitors in the world of photovoltaic solar cells.

1. Introduction applications, the task becomes more difficult. Double perovskite halide
compounds like Cs2 AgBiX6 (X = Cl and Br) attracted significant interest
The crises of energy and variation in climate related to the use of as compared to the solar absorbent material CH3 NH3 PbI3 (MAPI) which
traditional fossil fuels requires the development of renewable energy have Pb and are not stable [16]. Dan and his co-workers used density
technologies. Hybrid organic–inorganic halide perovskites CH3 NH3 Pb functional theory (DFT) to predict the thermodynamic stability of many
X3 (X = Cl, Br and I) has attracted a wide attention in the applications of double perovskite halides [17].
highly efficient solar cell applications like generation of solar hydrogen Due to their non toxic nature and 3-dimensional all double per-
and solar fuel power [1–3]. However due to the moisture and temper-
ovskite inorganic materials shows a lot of attention to replace lead
ature sensitivity Lead-based halide perovskites have stability problems
based perovskite material. Recently, Giustino and Snaith predicted new
and the presence of toxic element (lead), the large-scale applications of
elements to form halide double perovskites 15 . From there proposed
these materials are limited. Thus in order to overcome these problems
materials we chose one class as A1+ B1+ B3+ X1− except F and I due
it is needed to find Pb-free and stable materials as a replacement. In 2 6
this way double perovskite halide attracted a lot of attention [4–15]. to the large bandgap instability respectively. We examined the direct
The halide double perovskites is a huge class of quaternary halides. bandgap and stable double perovskite material A1+ 2
B1+ B3+ X1−
6
(A1+
2
=
1+ 3+ 1−
Cs, B = Li, Na, B = Tl, Sb, Bi, and X6 = Cl, Br) whose prospective
These materials’s extensive geometric range opens up possibilities for
novel solar and photovoltaic materials. However, when a huge number view of crystal structures is shown in Fig. 1. We studied the structural,
of compounds are evaluated to determine which are the most promising electronic, elastic, thermal and optical properties of our predicted
in terms of energy, structure, and electrical characteristics for solar cell materials having bandgap closer as MAPI.

∗ Corresponding author.
E-mail addresses: yasir.saeed@kaust.edu.sa, yasirsaeedphy@aust.edu.pk (Y. Saeed).

https://doi.org/10.1016/j.mssp.2022.106993
Received 4 January 2022; Received in revised form 4 June 2022; Accepted 20 July 2022
Available online 11 August 2022
1369-8001/© 2022 Elsevier Ltd. All rights reserved.
M. Zia ur Rehman et al. Materials Science in Semiconductor Processing 151 (2022) 106993

Table 1
Optimized lattice constant a (Å), Bulk modulus B (GPa) and Bandgap E𝑔 (eV) of studied
double perovskite A1+
2
B1+ B3+ X1−
6
.
Compounds a B E𝑔
Cs2 LiSbCl6 10.54 29.20 2.889
Cs2 LiBiCl6 10.70 27.76 3.604
Cs2 LiTlCl6 10.40 29.82 1.656
Cs2 LiSbBr6 11.08 24.37 2.284
Cs2 LiBiBr6 11.23 22.98 2.912
Cs2 LiTlBr6 10.96 23.83 0.654
1.817a
Cs2 NaSbCl6 10.69 27.90 2.980
Cs2 NaBiCl6 10.83 26.75 3.660
Cs2 NaTlCl6 10.56 27.68 1.537
Cs2 NaSbBr6 11.23 22.67 2.904
Cs2 NaBiBr6 11.37 22.51 2.972
Cs2 NaTlBr6 11.13 22.35 0.573
1.827a
a
(Values of bandgap with mBJ + SOC).

Fig. 1. Prospective view of crystal structures A1+

2
B1+ B3+ X1−
6
where B+1 = Na, Li B+3 =
Tl, Sb, Bi X6 = Cl, Br.

2. Computational detail

We performed our calculations by making use of full-potential

linearized augmented plane wave plus local orbitals (FP-LAPW+lo)
technique which is the part of DFT by using Wien2k program [18].
Structural, electronic and thermodynamic properties are examined by
employing generalized gradient approximation (WC-GGA) that is a
more accurate exchange–correlation potential flavor [19]. We applied
the modified Becke–Johnson (mBJ) plan across the WC-GGA to obtain
accurate bandgap [20,21]. Compared with experimental value, the mBJ
plan produced encouraging band structures and values of the bandgap
for lead halide perovskites and other semiconductors in the past [22–
32]. The scheme mBJ across WC-GGA gives results relative to the
experimental results for Cs2 AgBiX6 (X = Cl and Br) and then we applied
this scheme on our guessed compounds A1+ 2
B1+ B3+ X1−
6
. With k-mesh of
13 × 13 × 13 and finer k- mesh of 24 × 24 × 24 electronic and optical
properties are calculated respectively. By using energy convergence
tolerance of 10−5 Ry all structures are optimized. Furthermore, ab
initio molecular dynamics simulations are performed to investigate the
stability of the hetero-structures with an 8 × 8 × 8 supercell. The total
time and time step are set as 5 × 10−12 sec [33].
3. Results and discussion
To understand various physical properties of a compound the struc-
tural parameters play a major role. All twelve possible compounds
of our guessed double perovskites A1+ B1+ B3+ X1− (A1+ = Cs, B1+ = Li,
2 6 2 this information further can help to design solid state devices such as
Na, B3+ = Tl, Sb, Bi, and X1−
6
= Cl, Br) are classified into 2 classes i.e
Li and Na-based compounds. We obtained structural parameters such
as bulk modulus B (GPa) and lattice constant a (Å) for A1+ 2
B1+ B3+ X1−
6 = Cl, Br to examine their electronic behavior. The bandgap of all the
by volume optimization. As a starting point experimental values of
lattice parameter of Cs2 AgBiX6 (X = Cl and Br) are used. In Table 1
the structural parameters of possible compounds are shown which are
obtained by using he Birch–Murnaghan’s equation of states [34]. For
all compounds the optimized lattice constants are between 10.40 Å to
11.37 Å which are close to other experimentally synthesized double
perovskites such as Cs2 AgBiCl6 and Cs2 AgBiBr6 having lattice constants
10.77 Å and 11.27 Å respectively [16]. For Cs2 LiTlCl6 optimized B
is 29.82 GPa which is largest as compared to all other compounds.
While for Cs2 NaBiBr6 value of B is smallest as 22.51 GPa that shows
Fig. 2. Electron charge density of (a) Cs2 LiTlBr6 and (b) Cs2 NaTlBr6 in crystallographic
plane (110).
the hardness of this material. To compare these optimized compounds,
the experimental or theoretical data is not available.
To examine the origin of chemical bond between all the atoms
of both Cs2 LiTlCl6 and Cs2 NaTlCl6 the 2D electronic charge density
contours along (110) plane is investigated which is shown in Fig. 2.
In case of Cs2 LiTlBr6 the strong distribution and overlapped contours
among Tl and Br display a covalent bonding. While the transfer of large
charge and lost overlapped counters among Cs and Li atoms display
ionic bonding. Similarly in In case of Cs2 NaTlBr6 the strong distribution
and overlapped contours among Tl and Br display a covalent bond.
While transfer of large charge and lost overlapped counters between
Cs and Na atoms results in ionic bonding.
Band structure plays an important role in order to study the ma-
terial’s electronic behavior. By using band structure like metallic or
semiconducting etc we can examine the material’s electronic nature.
The physical properties of solids like optical behavior and resistivity
can be successfully explained from the electronic band structure and
transistors and solar cells etc. That is why we computed the band struc-
ture of Cs2 LiB3+ X1− and Cs2 NaB3+ X1− where B3 + = Tl, Sb, Bi and X1−
6 6 6
compounds were calculated by simple scf without including spin–orbit
coupling (SOC). Only those materials which have bandgap less than 1
eV were further studied with SOC and top of it we add mBJ approach
to correct the bandgap value in order to meet experimental values. As
a benchmark, We first re-calculate Cs2 AgBiCl6 and Cs2 AgBiBr6 values
of experimental bandgap, which are 2.77 eV and 2.19 eV respectively
that are reproduced with [16]. Our calculated values of the bandgap
for Cs2 AgBiBr6 without SOC is 1.16 eV, with SOC is 0.961 eV, and
with mBJ+SOC is 2.165 eV. On the other hand the bandgap values for
Cs2 AgBiCl6 without SOC is 1.685 eV, with SOC is 1.398 eV, and with

2
M. Zia ur Rehman et al.
Fig. 3. The computed BS of (a) Cs2 LiTlBr6 and (b) Cs2 NaTlBr6 without and with SOC.
mBJ+SOC is 2.63 eV. As we have calculated recently the bandgaps for
Cs2 (Li/Na)GaBr6 with mBJ+SOC to get the band gap values close to the
experimental value of MAPI and we obtained direct bandgap at gamma-
point that are similar to the MAPI [35]. Hence, we conclude that in the
double perovskites the FP-LAPW+lo technique underestimate values of
the bandgap substantially until adding mBJ+SOC. Thus our objective
is to obtain a material which is free from lead and having value of
the bandgap nearly equal to 1.6 eV which replaces MAPI at room
temperature [15].
For all materials calculated values of the bandgap without SOC
are listed in Table 1. After examining TABLE 1, Only Cs2 LiTlBr6 and
Cs2 NaTlBr6 have small values of the bandgap without SOC 0.654 eV
3
Materials Science in Semiconductor Processing 151 (2022) 106993
Table 2
The computed effective masses for electrons and holes of Cs2 LiTlBr6 and Cs2 NaTlBr6
without SOC with SOC and with mBJ + SOC.
Compound m∗𝑒 m∗ℎ
Without SOC 0.744 1.52
Cs2 LiTlBr6 With SOC 0.530 1.26
With mBJ + SOC 0.671 1.78
Without SOC 0.831 1.68
Cs2 NaTlBr6 With SOC 0.536 1.37
With mBJ + SOC 0.724 1.72
and 0.573 eV, respectively. On the other hand values of the bandgap
of rest compounds exceeding 1.4 eV. If we apply mBJ+SOC, than these
materials shows very large bandgap and not suitable for solar cell
applications.
We expanded our further study to focus only on Cs2 LiTlBr6 and
Cs2 NaTlBr6 compounds. We computed values of the bandgap for both
materials with and without SOC as given in Fig. 3. Values of the
bandgap for Cs2 LiTlBr6 without SOC is 0.654 eV (black color) and with
SOC is 0.561 eV (red color) as shown in Fig. 3(a). While for Cs2 NaTlBr6
the bandgap value without SOC is 0.573 (black color) and with SOC is
0.490 eV (red color) as shown in Fig. 3(b). We observed a small re-
duction in the bandgap value up to 93 meV and 83 meV for Cs2 LiTlBr6
and Cs2 NaTlBr6 respectively by applying SOC. After that, band struc-
tures for Cs2 LiTlBr6 and Cs2 NaTlBr6 are calculated with mBJ+SOC
(see Fig. 4(a,b)). For Cs2 LiTlBr6 and Cs2 NaTlBr6 the calculated direct
bandgap values are 1.817 eV and 1.827 eV, respectively.
The bandgap values of Cs2 LiTlBr6 and Cs2 NaTlBr6 are closer to
the experimentally calculated values of CH3 NH3 PbI3 (Cl, Br). For the
bandgap range between 1.0 and 1.7 eV we can make an efficient
semiconductor solar. In this range of the bandgap, electrons can be
released without producing huge amount of heat. Although the recently
studied double perovskite has a direct bandgap and the bandgap value
exceeds the range 9 . While other have values of the bandgap within the
mentioned range, although nature of the bandgap is indirect therefore
is not suitable for solar cell applications. further, pressure-induced
bandgap tuning can be possible to get bandgap close to 1.5 eV.
For capable electronic and optoelectronic devices high carrier mo-
bility is strongly demanded [36]. Transport of charge carriers is greater
because of smaller effective mass. Effective mass of MAPI is less than
0.2 m𝑒 and its carrier mobility is less than 100 cm2 V−1 s−1 which
is modest compared to traditional semi- conductors like GaAs or Si
(> 1000 cm2 V−1 s−1 ) [37,38]. In perovskite solar cell the effective
mass of MAPI can lead to am-bipolar conductivity and it promotes the
p–i–n junction solar cell [39]. Basically there are two types of charge
carriers i.e electrons and holes. We indicated both of them separately
in our study. The electron’s effective mass (m*𝑒 ) and hole’s effective
mass (m*ℎ ) for both Cs2 LiTlBr6 and Cs2 NaTlBr6 without SOC, with SOC
and with mBJ+SOC are given in Table 2. It is clear from Table 2 that
(m*𝑒 ) of Cs2 LiTlBr6 and Cs2 NaTlBr6 are 0.671 and 0.724 respectively
which are less than that of Si (1.09) therefore it is expected that the
carrier mobility of both materials is greater than Si [40]. We have
used the conduction and valance band fitting to parabola by calcu-
2 𝐸(𝑘)
lating the effective mass by using the equation 𝑚∗ 1
= ℏ12 𝜕 𝜕𝑘2 , in this
equation 𝒌 and E(𝒌) are the wave vector and the energy corresponding
to 𝒌, respectively. Smaller the effective mass shows higher will be
carrier mobilities, here Cs2 LiTlBr6 is strongly desirable for competent
electronic and optoelectronic devices application [41].
In order find out the contribution of atoms (Cs, Li, Na, Tl, Br) into
VBM and CBM we have calculated the density of states of both materi-
als. Total density of states (TDOS) and partial density of states (PDOS)
of Cs2 LiTlBr6 and Cs2 NaTlBr6 is given in Figs. 4 and 5 respectively. In
Fig. 4(a) and (b) we can see that the VBM is entirely contributed in Br
atom in case of both materials. Although a CBM is mutually shared in Tl
and Br atoms. While in both materials the Li and Na atoms are greatly
M. Zia ur Rehman et al.
Fig. 4. The computed band structure and TDOS of (a) Cs2 LiTlBr6 and (b) Cs2 NaTlBr6
using mBJ+SOC.
occupied in the bandgap value. In order to find out, which orbital of
Br or Tl plays a role in the VBM and CBM, we additionally calculated
(PDOS), as shown in Fig. 5(a) for (Cs2 LiTlBr6 ) and in Fig. 5(b) for
(Cs2 NaTlBr6 ). We can see in Fig. 5(a) that Li-p orbital dominants in
comparison to s and d orbitals in CBM and VBM, although compared to
other atoms the magnitude of Li is very small. s-orbital of Tl atom also
shows its significance in CBM, but contribution of p and d is largely but
minute in VBM. Br’s p𝑥 + p𝑦 orbital plays an important role in majority
peaks in VBM. Br’s p-orbital is occupied all the VBM up to 2 eV. While
Br’s d-orbital has no contribution in VBM and CBM. Also Cs’s p-orbital
has larger contribution in VBM compared of Li and Tl. We observed
the similar behavior of Cs2 NaTlBr6 in PDOS but s-orbital of Tl and p-
orbital of Br are completely dominated in CBM and VBM respectively
is dominated see Fig. 5(b).
By employing the dielectric function i.e 𝜀(𝜔) = 𝜀1 (𝜔) + 𝑖𝜀2 (𝜔)
the linear optical properties can be described [42]. The combined
DOS and transition momentum matrix components are closely related
to the dielectric characteristics 𝜀2 (𝜔). We can obtain the real part
of the dielectric function 𝜀1 (𝜔) from the 𝜀2 (𝜔) by Kramers–Kronig’s
relationship [43]. By the dispersion of real and imaginary components
of dielectric characteristics we can compute other optical properties
like index of refraction, optical conductivity, absorption coefficient and
reflectivity.
For Cs2 LiTlBr6 and Cs2 NaTlBr6 optical characteristics are examined
by computing the optical parameters such as index of refraction (n),
extinction coefficient (k) absorption coefficient 𝐼(𝜔), optical conduc-
tivity 𝜎(𝜔) and reflectivity 𝑅(𝜔) shown in Fig. 6. For Cs2 LiTlBr6 and
Cs2 NaTlBr6 the static dielectric constant 𝜀(0) are 1.6 eV and 1.7 eV
respectively. We have observed similar results for Cs2 (Li/Na)GaBr6
recently [35].
4
Materials Science in Semiconductor Processing 151 (2022) 106993
Fig. 5. Computed PDOS of (a) Cs2 LiTlBr6 and (b) Cs2 NaTlBr6 with mBJ+SOC.
It is clear from Fig. 6(a) that for both materials the static index of
refraction n(0) is 1.95 (Li-based) and 1.6 (Na-based). Cs2 LiTlBr6 𝑛(𝜔)’s
highest value is 1.8 eV and 𝑘(𝜔)’s highest value is 2.6 eV, while for
Cs2 NaTlBr6 the value 𝑛(𝜔) is 2.5 eV the value of 𝑘(𝜔) is 3.2 eV. From
Fig. 6(b) it is clear that for Cs2 LiTlBr6 maximum of optical conductivity
(𝜎) of 650 (Ω cm)−1 is about at 2.6 eV and for Cs2 NaTlBr6 first peak
of 500 [Ω cm]−1 at 3 eV. Thus optical conductivity of Cs2 NaTlBr6 is
high in the visible light region (1.77 (700 nm) to 3.1 eV (400 nm), and
is important for solar cell. The solar energy conversion efficiency can
be describes from absorption coefficient and describes the penetration
of specific light’s frequency into the material before absorption. For
Cs2 LiTlBr6 and Cs2 NaTlBr6 the coefficient of absorption spectrum 𝐼(𝜔),
maximum arises of 12×104 cm−1 at 2.6 eV (477 nm) and of 11×104 cm−1
at 3.2 eV, respectively as shown in Fig. 6(c). Which is comparable
to MAPI 104 − 105 cm−1 . Values of coefficient of absorption increases
rapidly when incident photon reaching the absorption edge. In the
visible region absorption of Cs2 LiTlBr6 is higher than Cs2 NaTlBr6 . While
for Cs2 LiTlBr6 and Cs2 NaTlBr6 maximum of reflectivity 𝑅(𝜔) is 13.5%
at about 1.6 eV and 9% at 2.2 eV respectively as shown in Fig. 6(d).
For desirable practical applications of material the effective elastic
constants play an important role. The elastic constant describes the
stability of structure and material’s response to external forces. For
M. Zia ur Rehman et al. Materials Science in Semiconductor Processing 151 (2022) 106993

Fig. 6. The computed optical properties of Cs2 LiTlBr6 (solid lines) and Cs2 NaTlBr6 (dotted line).

Table 3
The computed values of elastic properties for Cs2 LiTlBr6 and Cs2 NaTlBr6 .
Cs2 LiTlBr6 Cs2 NaTlBr6
C11 45.67 45.09
C12 13.68 10.98
C44 9.83 7.82
G𝑉 12.29 11.51
G𝑅 11.56 9.98
G𝐻 11.92 10.57
Y 31.57 29.43
B/G 2.04 2.11
C∕∕ 3.85 3.16
𝜈 0.28 0.28
A 0.61 0.45
C∕ 15.99 17.05

Fig. 7. Thermal stability and phonon band structures of (a,c) Cs2 NaTlBr6 and (b,d)
Cs2 LiTlBr6 .
Cs2 LiTlBr6 and Cs2 NaTlBr6 the calculated elastic constants are listed
in Table 3. To compare our predicted values the experimental results
are not available. Both materials fulfill the stability criteria of Born for
cubic crystals that is C11 > 0, C44 > 0, C11 + 2C12 > 0, C11 − C12 > 0
and C12 < B < C11 [44]. This proves that both the mentioned materials
are elastically stable to deformation forces.
In order to compute the mechanical properties the elastic constant
are under the study using standard relations which are listed in Ta-
ble 3 [45,46]. The shear modulus G𝐻 is used to measure the material’s
plastic deformation to applied stress. For Cs2 LiTlBr6 the higher values
of Young modulus (Y) and shear modulus (G𝐻 ) verifies that it offers
greater resistance against the plastic deformation and it is stiffer as
compared to Cs2 NaTlBr6 . B/G (Pugh ratio) indicates materials’s ductile
and brittle behavior [47]. From Table 3 it is clear that for both
materials the B/G ratio is larger than 1.75 (critical value) therefore
these materials are ductile. The positive or negative values of Cauchy’s
pressure (C∕∕ = C12 − C44 ) also indicates the ductile or brittle nature
of materials. Thus positive value of C∕∕ (in Table 3) also indicate the
ductility of Cs2 LiTlBr6 and Cs2 NaTlBr6 .
Poisson’s ratio (𝜈) indicates the crystal’s stability against compress-
ibility. Both materials are stable against shear stress because of smaller
values of (𝜈). For Cs2 LiTlBr6 and Cs2 NaTlBr6 values of anisotropic
constant (A) for are given in Table 3. Material’s degree of anisotropy
can be measured by the deviation of A from unity. From the table it is
clear that anisotropic factor is less than unity, therefore properties of
materials change in different crystallographic directions. Shear constant
C∕ indicates the material’s the dynamical stability against tetragonal
distortion. C∕ must be greater than zero (positive values) for dynamical
stability [48]. Values of C∕ for both materials are greater than 0 as
mentioned is Table 3 and this proves that both are stable mechanically.
We have calculated the thermal stability and phonon band structure
of both Cs2 NaTlBr6 and Cs2 LiTlBr6 to check stability by applying ab-
initio molecular dynamics simulations [49] at temperature of 300 K for
total time of 6 ps with a time interval of 1 fs as shown in Fig. 7(a,b), its
cleared that both materials retain their geometries without any struc-
tural distortion. To further confirm the stability, we calculate phonon

5
M. Zia ur Rehman et al.
band structure for both compounds (shown in Fig. 7(c,d). We use the
supercell approach, as implemented in PHONOPY package [50,51], to
perform the relevant frozen-phonon calculations for both structures
under examined. For each of them, a 2 × 2 × 2 supercell was used
for the phonon calculations. Both the structures are dynamically stable
within the known numerical error of phonon calculations (≃ 0.1 THz,
or about 0.4 meV/atom for our structures) [52–55].
4. Conclusion
In this article the double perovskites A1+
2
B1+ B3+ X1−
6
, where A1+
2
= Cs,
B1+ = Li, Na, B3+ = Tl, Sb, Bi, and X1−
6
= Cl, Br have been investigated to
study the electronic, optical and elastic properties. The lattice constants
of A1+
2
B1+ B3+ X1−
6
were found after carefully optimization of the volume.
By calculating the bandgap of all materials, we concluded that only
Cs2 LiTlBr6 and Cs2 NaTlBr6 has small values of the bandgap 0.654 eV
and 0.573 eV, respectively. These values of the bandgap are decreased
from 0.654 eV to 0.561 eV and 0.573 to 0.38 eV due to SOC and we
observed a small reduction in the bandgap value up to 9.3 meV and
8.3 meV for Cs2 LiTlBr6 and Cs2 NaTlBr6 respectively. By applying mBJ
+ SOC we obtained values of direct bandgap of 1.817 eV for Cs2 LiTlBr6
and 1.827 eV for Cs2 NaTlBr6 that are close to the experimental bandgap
of MAPI. Effective mass of electron (m*𝑒 ) for Cs2 LiTlBr6 and Cs2 NaTlBr6
are 0.671 and 0.724, respectively, which are less than that of Si (1.09)
therefore it is expected that the carrier mobility of both materials is
greater than Si which is strongly demanded for capably optoelectronic
devices. TDOS indicates that Br has major contribution in VBM while
the contribution of Tl is in CBM. While (PDOS) indicates that Br-p and
Tl-s orbitals are contributing. By calculating the optical spectra we con-
clude that Cs2 LiTlBr6 has more absorption coefficient as compared to
Cs2 NaTlBr6 . These two materials are thermodynamically and elastically
stable as well. Thus we concluded that Cs2 LiTlBr6 and Cs2 NaTlBr6 are
more suitable candidates for solar cell application among our studied
double perovskite compounds and these materials should be significant
competitors in the world of lead-free hybrid perovskite solar cell in
future.
CRediT authorship contribution statement
M. Zia ur Rehman: Investigation. Shaimaa A.M. Abdelmohsen:
Investigation. Eman A. Mahmoud: Investigation. M. Usman Saeed:
Investigation. M. Idress: Methodology, Conceptualization. M. Shafiq:
Writing –review & editing. B. Amin: Writing –review & editing. Y.
Saeed: Supervision, Writing – review & editing, Conceptualization.
Declaration of competing interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared to
influence the work reported in this paper.
Data availability
No data was used for the research described in the article.
Acknowledgments
The authors express their gratitude to Princess Nourah bint Abdul-
rahman University Researchers Supporting Project, Saudi Arabia (Grant
No. PNURSP2022R61), Princess Nourah bint Abdulrahman University,
Riyadh, Saudi Arabia. The authors would like to thank IT depart-
ment of National Center for Physics (NCP), Islamabad for supplying
computational resources.
Materials Science in Semiconductor Processing 151 (2022) 106993
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